U.S. patent application number 11/268848 was filed with the patent office on 2007-05-10 for half metallocene catalyst and process for preparing syndiotactic styren polymer using the same.
Invention is credited to You-mi Jeong, Young-jo Kim, Min-hyung Lee, Doh-yeon Park.
Application Number | 20070105710 11/268848 |
Document ID | / |
Family ID | 38004510 |
Filed Date | 2007-05-10 |
United States Patent
Application |
20070105710 |
Kind Code |
A1 |
Kim; Young-jo ; et
al. |
May 10, 2007 |
Half metallocene catalyst and process for preparing syndiotactic
styren polymer using the same
Abstract
The present invention relates to a transition metal half
metallocene catalyst with a noble structure for preparing
syndiotatic styrene polymer having high activity, superior
stereoregularity, high melting point and broad molecular weight
distribution and a process for preparing styrene polymer using the
same. The present invention provides a half metallocene catalyst
having a single nucleus structure, in which a transition metal in
Groups 3 to 10 on the periodic table is connected to a
cycloalkanedienyl group or its derivative forming 5-coordinate bond
on a side thereof and to any one of triethanolamine,
N-alkyldiethanolamine and N-dialkylethanolamine group, all of which
have a plurality of binding sites and high steric hinderance, on
the other side thereof. The noble metallocene catalyst according to
the present invention is useful for preparing highly syndiotatic
vinyl aromatic polymer with broad molecular weight distribution and
high activity.
Inventors: |
Kim; Young-jo; (Daejeon,
KR) ; Park; Doh-yeon; (Daejeon, KR) ; Jeong;
You-mi; (Daejeon, KR) ; Lee; Min-hyung;
(Daejeon, KR) |
Correspondence
Address: |
CANTOR COLBURN, LLP
55 GRIFFIN ROAD SOUTH
BLOOMFIELD
CT
06002
US
|
Family ID: |
38004510 |
Appl. No.: |
11/268848 |
Filed: |
November 8, 2005 |
Current U.S.
Class: |
502/152 ;
526/160; 526/346; 526/901 |
Current CPC
Class: |
C08F 4/6592 20130101;
Y10S 526/943 20130101; C08F 4/65912 20130101; C08F 112/08 20130101;
C08F 112/08 20130101; C08F 4/6592 20130101 |
Class at
Publication: |
502/152 ;
526/160; 526/901; 526/346 |
International
Class: |
B01J 31/00 20060101
B01J031/00 |
Claims
1. A half metallocene catalyst represented by the formula 1, 2 or
3: ##STR15## wherein, M.sup.1, M.sup.2 and M.sup.3 are transition
metals independently selected from the group consisting of atoms in
Groups 3, 4, 5, 6, 7, 8, 9, 10 of the Periodic Table, and Each of
L.sup.1, L.sup.2 and L.sup.3 is a cycloalkanedienyl ligand
represented by the formula 4, 5, 6, 7 or 8: ##STR16## wherein,
R.sup.1 R.sup.2 R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7,
R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, and R.sup.13 are
independently hydrogen atom, halogen, alkyl, C.sub.3-20 cycloalkyl,
C.sub.2-20 alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl,
alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl, arylsilyl,
arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl,
aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or
arylphosphinoalkyl group (here, the alkyl group is c.sub.1-20
hydrocarbon group having straight or branch structure and the aryl
group is C.sub.6-40 aromatic or heteroaromatic group) and each of m
and n is an integer of 1 or more; X.sup.1, X.sup.2, and X.sup.3,
which are .sigma.-ligand functional groups, are independently
hydrogen atom, halogen, alkyl, C.sub.3-20 cycloalkyl, alkylsilyl,
C.sub.2-20 alkenyl, alkoxy, alkenyloxy, thioalkoxy, alkylsiloxy,
amide, alkoxyalcohol, alcoholamine, aryl, alkylaryl, arylalkyl,
arylsilyl, haloaryl, aryloxy, arylalkoxy, thioaryloxy,
arylalkylsiloxy, arylamide, arylalkylamide, aryloxoalcohol,
alcohoarylamine, or arylaminoaryloxy group (here, the alkyl group
is c.sub.1-20 hydrocarbon group having straight or branch structure
and the aryl group is C.sub.6-40 aromatic or hetero aromatic group)
A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are
functional groups bounded to a central metal and are independently
oxygen atom or sulfur atom; D.sup.1, D.sup.2, D.sup.3, D.sup.4,
D.sup.5 and D.sup.6 are functional groups and are independently
alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20 alkenyl or C.sub.6-40 aryl
group; E.sup.1, E.sup.2, E.sup.3, E.sup.4, E.sup.5, E.sup.6,
E.sup.7, E.sup.8, E.sup.9, E.sup.10, E.sup.11, and E.sup.12 are
independently hydrogen atom, halogen, alkyl, C.sub.3-20 cycloalkyl,
C.sub.2-20 alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl,
alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl, arylsilyl,
arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl,
aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or
arylphosphinoalkyl group (here, the alkyl group is c.sub.1-20
hydrocarbon group having straight or branch structure and the aryl
group is C.sub.6-40 aromatic or heteroaromatic group) Q.sup.1,
Q.sup.2 and Q.sup.3 are independently nitrogen or phosphorous; and
Z.sup.1, Z.sup.2 and Z.sup.3 are independently hydrogen atom,
alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20 alkenyl, alkylsilyl,
haloalkyl, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl,
aminoalkyl, alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl,
arylsilyl, arylalkylsilyl, haloaryl, aryloxoalkyl,
thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy,
arylsiloxalkyl, arylsiloxoaryl, arylamino, arylaminoalkyl,
arylaminoaryl or arylphosphinoalkyl group (here, the alkyl group is
a C.sub.1-20 hydrocarbon group having the straight or branch
structure and the aryl group is a C.sub.6-40 aromatic or
heteroaromatic group).
2. The half metallocene catalyst of claim 1, wherein the half
metallocene catalyst is represented by any one of the formulas 9,
10, 11, 12, 13, 14, 15, 16 and 17: ##STR17## ##STR18##
3. A process for preparing a styrene polymer by homopolymerizing
styrene monomers (styrene or styrene derivatives), copolymerizing
styrene monomers (styrene and styrene derivatives) or
copolymerizing the styrene monomers with olefins monomers (olefin
and olefin derivatives) using a catalyst system, wherein the
catalyst system comprises: a main catalyst of the metallocene
compound of claim 1; and one or more cocatalysts selected from the
group consisting of alkylaluminoxane of the formula 18,
alkylaluminum of the formula 19 and weak coordinate Lewis acid,
##STR19## wherein, R.sup.14 is a hydrogen atom, substituted or
unsubstituted alkyl, substituted or unsubstituted C.sub.3-20
cycloalkyl, aryl, alkylaryl or arylalkyl group; and R.sup.15,
R.sup.16 and R.sup.17 are independently hydrogen atom, halogen,
substituted or unsubstituted alkyl, substituted or unsubstituted
C.sub.3-20 cycloalkyl, aryl, alkylaryl or arylalkyl group (here,
the alkyl group is a C.sub.1-20 hydrocarbon group having the
straight or branch structure and the aryl group is a C.sub.6-40
aromatic or heteroaromatic group) where at least one of the
R.sup.15, R.sup.16 and R.sup.17 includes the alkyl group and n is
an integer ranging from 1 to 100.
4. The process of claim 3, wherein the half metallocene compound
includes a central metal of 10.sup.-8 to 1.0M.
5. The process of claim 3, wherein a mole ratio of the
alkylalumonoxane to the half metallocene compound ranges from 1:1
to 10.sup.6:1.
6. The process of claim 3, wherein a mole ratio of the
alkylaluminum to the half metallocene compound ranges from 1:1 to
10.sup.4:1.
7. The process of claim 3, wherein a mole ratio of the weak
coordinate Lewis acid to the half metallocene compound ranges from
0.1:1 to 50:1.
8. The process of claim 3, wherein the polymerization is conducted
at a temperature in the range of from -80 to 200.degree. C.
9. The process of claim 3, wherein a styrene pressure is in the
range of from 0.01 to 20 atm when polymerization for
homopolymerizing the styrene monomers is conducted.
10. The method of claim 3, wherein polymerization pressure is in
the range of from 1 to 1000 atm including the pressure of
comonomers.
11. The process of claim 3, wherein each of the styrene derivatives
has one or more substituent on a benzene ring, and the substituent
is selected from the group consisting of halogen, alkyl, alkoxy,
ester, thioalkoxy, sillyl, tin, amine, phosphine, halogenated
alkyl, C.sub.2-20 vinyl, aryl, vinylaryl, alkylaryl, and arylalkyl
group, where the alkyl group is C.sub.1-10 hydrocarbon group having
the straight or branch structure, and the aryl group is C.sub.4-60
aromatic or heteroaromatic group.
12. The process of claim 3, wherein the olefin monomer is selected
from the group consisting of C.sub.2-20 cycloolefin, cyclodiolefin
and C.sub.4-20 diolefin.
13. The process of claim 3, wherein the polymer is styrene
homopolymer, styrene derivative homopolymer, copolymer of styrene
and its derivative, copolymer of styrene and olefin, or copolymer
of styrene derivative and olefin.
14. The process of claim 3, wherein the polymerization is conducted
by a slurry phase polymerization, a liquid phase polymerization, a
gas phase polymerization and a bulk state polymerization.
15. The process of claim 3, wherein the polymerization is conducted
by sequentially injecting solvent, the styrene monomer, the
alkylaluminum, the cocatalyst and the half metallocene compound
into a reactor.
16. The process of claim 3, wherein the main catalyst is activated
by the cocatalyst selected from the group consisting of
alkylaluminoxane of the formula 18, alkylaluminum of the formula 19
and weak coordinate Lewis acid in advance, and then the activated
main catalyst is introduced into a reactor containing the monomers
therein.
17. The process of claim 3, wherein the polymerizing comprises the
steps of: i) applying alkylaluminum to the styrene monomers; ii)
activating the metallocene compound serving as the main catalyst by
bring the metallocene compound into contact with the cocatalyst;
and iii) introducing the activated main catalyst of step ii) into a
reactor charged with the styrene monomers and alkaylaluminum to
cause polymerization.
18. The process of claim 3, wherein activation of the main catalyst
is performed at a temperature in the range of from 0 to 150.degree.
C. for 0.1 to 240 minutes.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a metallocene catalyst for
preparing vinyl aromatic polymers and a method for styrene
polymerization using the same, and more particularly to a
transition metal half metallocene catalyst with a noble structure
for preparing syndiotactic styrene polymers having high activity,
superior stereoregularity, high melting point and broad molecular
weight distribution and a method for preparing styrene polymers
using the same.
[0003] 2. Background of the Related Art
[0004] Such syndiotactic polystyrene can be generally prepared
using a metallocene catalyst composed of a Group 4 transition metal
in the periodic table, such as titanium, zirconium or hafnium, and
one or two cycloalkanedienyl groups. The cycloalkandienyl group
includes cyclopentadienyl, indenyl, fluorenyl group and their
derivatives.
[0005] For example, Ishihara et al. from Idemitus Kosan Co. has
proposed that syndiotatic polysterene can be synthesized with high
yield by using a catalyst system prepared by combining a titanium
compound with an alkyl aluminum derivative in 1985. It was the
first metalloscene catalyst for synthesizing syndiotatic
polystyrene. U.S. Pat. No. 4,680,353 has disclosed a process for
synthesizing syndiotactic polystyrene using a catalyst composed of
a Group 4 atom as a metal center and various substituents including
alkyl group and alkoxyl group in the presence of a cocatalyst such
as alkylaluminum derivatives. The process disclosed in this patent,
however, is disadvantageous in that it requires a complicated
polymer purification process after polymerization to obtain pure
styrene polymer due to the use of large amounts of the
alkylaluminum derivatives for the polymerization and the catalyst
used in the polymerization exhibits the low catalytic activity, for
example 0.8 kg-PS(mmol-metal) (mol-styrene) or lower.
[0006] U.S. Pat. No. 5,206,197 has disclosed a process for
synthesizing polystyren with a high degree of syndiotacticity using
a catalyst composed of a metal selected from the group consisting
of Groups 3 to 10 atoms in the periodic table, a cationic organic
metal compound with or without having cyclopentadienyl group, and
an anion organic compound for stabilizing the cationic organic
metal compound which does not affect the polymerization activity in
the presence of a small amount of alkylaluminum. This process,
however, is also disadvantageous in that it requires the high mole
ratio of styrene to catalyst, ranging from 3,500:1 to 500,000:1,
resulting in a large amount of styrene residues left without taking
part in polymerization.
[0007] U.S. Pat. No. 5,597,875 has disclosed a reactor for
continuously producing syndiotactic polystyrene using a catalyst
composed of a first component and a second component where the
first component is a metal center selected from the group
consisting of Groups 3 to 6 atoms and the second component is
composed of an organic metal compound having various substituents
including alkyl group and alkoxy group, and alkyl derivatives, or
composed of cations from an organic metal compound and anions for
stabilizing the organic metal compound.
[0008] However, as described above, most of the studies for
preparation of polystyrene, which has disclosed so far, are
commonly focused on pursuing diversity of a catalyst, including
modifying cycloalkandienyl group bounded to a titanium atom by
imparting various types of substituent groups to the
cycloalkanedienyl group and substituting chloro group or methoxy
group bound to the titanium atom at a different position with a
different simple substituent.
[0009] For example, the inventors of the present application have
recently reported a process for preparing syndiotatic polystyren
having much higher activity and syndiotacticity as compared to the
conventional ones, using a half metalloscene catalyst in which
either chloro group or methoxy group is substituted with
ethanolamine group or N-alkyldiethanolamine group having a
plurality of binding sites, in the following international
journals: (1) Yongjo Kim, Eunkee Hong, Min Hyung Lee, Jindong Kim,
Yonggyu Han and Youngkyu Do, Organometallics 1999, 18, 36; (2)
Yongjo Kim and Youngkyu Do, Macromol. Rapid Comm. 2000, 21, 1148;
(3) Yongjo Kim, Yonggyu Han and Yongkyu Do, J. Organomet. Chem.
2001, 634, 19; and (4) Yongjo Kim, Yonggyu Han, Jeong-Wook Hwang,
Myong Won Kim and Yongkyu Do, Organometallics 2002, 21, 1127; and
(5) Yongjo Kim and Youngkyu Do, J. Organomet. Chem. 2002, 655, 186.
Further, the same process was issued as Korean Patent No. 0301135
(invented by Youngjo Kim, Min Hyung Lee, Yongkyu Do, Yi-Yeol Lyu,
Jin Hyung Lim and Hyun-Joon Kim). Korean Patent No. 0301135 has
disclosed a catalyst composed of a metal center selected from Group
4 atoms of the periodic table, either cycloalkandienyl group or its
derivative, and either triethanolamine group or N-alkylethanolamine
group, and a polymerization process using the same catalyst in the
presence of alkyl aluminum or one of its derivatives. Korean Patent
No. 0365869 by Yongjo Kim, Minhyung Lee, Sungjin Park, Youngkyu Do,
Sungwoong Yoon, Kiho Choi and Bogeun Song has disclosed a new
catalyst synthesized by imparting an expensive substituent with
high chirality to triethanolamine group and a process for
synthesizing syndiotatic polystyrene with high syndiotacticity
using the new catalyst. However, the catalysts disclosed in the two
Korean Patents above are disadvantageous in that they exhibit high
activity only in the presence of a large amount of alkyl aluminum
oxane and the constituent imparted to the triethanolamine group or
N-alkyldiethanolamine group is so expensive while they have an
advantage of having steric hindrance, meaning high production cost
for producing polystyren. For such reasons, it was difficult to
commercialize the catalysts.
[0010] Accordingly, there is still a need for a catalyst that can
be produced in low cost, easily treated and exhibit high activity
and stability, needing a small amount of cocatalyst such as alkyl
aluminum oxane.
SUMMARY OF THE INVENTION
[0011] The object of the present invention is to provide a new half
metallocene catalyst for synthesizing syndiotatic polystyrene with
high stereoregularity, high melting point and broad molecular
weight distribution in the presence of a small amount of
cocatalyst.
[0012] Another object of the present invention is to provide a
process for polymerizing styrene monomers and copolymerizing with
olefins using the metallocene catalyst.
[0013] Further another object f the present invention is to provide
a process for synthesizing styrene-based polymers such as
syndiotatic styrene polymers and styrene-olefin copolymers which
have high stereoregularity, high melting point and broad molecular
weight distribution, with high yield.
[0014] In order to achieve the objects and advantages above, the
inventors of the present application have developed a new catalyst
for preparing effectively styrene polymers with high
syndiotacticity by imparting a substituent, which is cheap and
capable of giving high steric hindrance, to triethanolamine group,
N-alkyldiethanolamine group or N-dialkylethanolamine group.
[0015] The new catalyst according to the present invention is
composed of a transition metal of Group 3 to 10 atoms in the
periodic table, cycloalkanedienyl group or its derivative bounded
to a side of the transition metal for inducing 775 combination, and
a ligand, such as triethnolamine, N-alkyldiethanol amine, or
N-dialkylethanolamine group, bounded to the other side of the
transition metal, where the ligand is combined with a substituent
having two or more coordination sites and giving high steric
hindrance, and has any one of the following formulas 1, 2, or 3:
##STR1##
[0016] where, in the formulas 1, 2 and 3, M.sup.1, M.sup.2 and
M.sup.3 are transition metals independently selected from the group
consisting of atoms in Groups 3, 4, 5, 6, 7, 8, 9, 10 on the
Periodic Table, and Each of L.sup.1, L.sup.2 and L.sup.3 is a
cycloalkanedienyl ligand represented by any one of the following
formulas 4, 5, 6, 7 or 8: ##STR2##
[0017] where in the formulas 4, 5, 6, 7 and 8, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9,
R.sup.10, R.sup.11, R.sup.12, and R.sup.13 are independently
hydrogen atom, halogen, alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20
alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy, amino,
alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl,
alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl, arylsilyl,
arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl,
aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or
arylphosphinoalkyl group (here, the alkyl group is C.sub.1-20
hydrocarbon group having either the straight or the branch
structure and the aryl group is C.sub.6-40 aromatic or
heteroaromatic group) and each of m and n is an integer of 1 or
more;
[0018] X.sup.1, X.sup.2, and X.sup.3, which are .sigma.-ligand
functional groups, are independently hydrogen atom, halogen, alkyl,
C.sub.3-20 cycloalkyl, alkylsilyl, C.sub.2-20 alkenyl, alkoxy,
alkenyloxy, thioalkoxy, alkylsiloxy, amide, alkoxyalcohol,
alcoholamine, aryl, alkylaryl, arylalkyl, arylsilyl, haloaryl,
aryloxy, arylalkoxy, thioaryloxy, arylalkylsiloxy, arylamide,
arylalkylamide, aryloxoalcohol, alcohoarylamine, or
arylaminoaryloxy group (here, the alkyl group is C.sub.1-20
hydrocarbon group having the straight or branch structure and the
aryl group is C.sub.6-40 aromatic or hetero aromatic group);
[0019] A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5 and A.sup.6 are
functional groups bounded to a central metal (the transition metal)
and are independently oxygen atom or sulfur atom;
[0020] D.sup.1, D.sup.2, D.sup.3, D.sup.4, D.sup.5 and D.sup.6 are
functional groups and are independently alkyl, C.sub.3-20
cycloalkyl, C.sub.2-20 alkenyl or C.sub.6-40 aryl group;
[0021] E.sup.1, E.sup.2, E.sup.3, E.sup.4, E.sup.5, E.sup.6,
E.sup.7, E.sup.8, E.sup.9, E.sup.10, E.sup.11, and E.sup.12 are
independently hydrogen atom, halogen, alkyl, C.sub.3-20 cycloalkyl,
C.sub.2-20 alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl,
alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl, arylsilyl,
arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl,
aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or
arylphosphinoalkyl group (here, the alkyl group is C.sub.1-20
hydrocarbon group having the straight or branch structure and the
aryl group is C.sub.6-40 aromatic or heteroaromatic group);
[0022] Q.sup.1, Q.sup.2 and Q.sup.3 are independently nitrogen or
phosphorous; and
[0023] Z.sup.1, Z.sup.2 and Z.sup.3 are independently hydrogen
atom, alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20 alkenyl, alkylsilyl,
haloalkyl, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl,
aminoalkyl, alkylphosphinoalkyl, aryl, arylalkyl, alkylaryl,
arylsilyl, arylalkylsilyl, haloaryl, aryloxoalkyl,
thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy,
arylsiloxalkyl, arylsiloxoaryl, arylamino, arylaminoalkyl,
arylaminoaryl or arylphosphinoalkyl group (here, the alkyl group is
C.sub.1-20 hydrocarbon group having the straight or branch
structure and the aryl group is C.sub.6-40 aromatic or
heteroaromatic group).
[0024] Particularly, in the formulas 1, 2 and 3, transannular
interactions of coordinate bonds preferably exist between M.sup.1
and Q.sup.1; M.sup.2 and Q.sup.2; and M.sup.3 and Q.sup.3.
[0025] The metallocene catalyst having the formula 1, 2 and 3 can
be preferably represented by any one of the following formulas 9,
10, 11, 12, 13, 14, 15, 16 or 17, and a structure of the chemical
compound corresponding to the formula 10 is analyzed by an X-ray
single crystal diffractometer and is shown in FIG. 1: ##STR3##
##STR4##
[0026] Further according to another embodiment of the present
invention, there is provided a process for synthesizing polystyrene
by homopolymerizing styrene monomers or copolymerizing styrene
monomers with olefin monomers in the presence of a catalyst system,
wherein the catalyst system comprises:
[0027] a) a main catalyst of a metallocene compound represented by
the formula 1, 2 or 3; and
[0028] b) one or more cocatalyst selected from the group consisting
of alkylaluminoxane of the formula 18, alkylaluminum of the formula
19 and weak coordinate Lewis acid: ##STR5##
[0029] wherein, R.sup.14 is a hydrogen atom, substituted or
unsubstituted alkyl, substituted or unsubstituted C.sub.3-20
cycloalkyl, aryl, alkylaryl or arylalkyl group; and R.sup.15,
R.sup.16 and R.sup.17 are independently hydrogen atom, halogen,
substituted or unsubstituted alkyl, substituted or unsubstituted
C.sub.3-20 cycloalkyl, aryl, alkylaryl or arylalkyl group (here,
the alkyl group is C.sub.1-20 hydrocarbon group having straight or
branch structure and the aryl group is C.sub.6-40 aromatic or
heteroaromatic group) where at least one of the R.sup.15, R.sup.16
and R.sup.17 includes the alkyl group and n is an integer ranging
from 1 to 100.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] The above and other objects, features and other advantages
of the present invention will be more clearly understood from the
following detailed description taken in conjunction with the
accompanying drawing, in which;
[0031] FIG. 1 is an X-ray photograph illustrating a single crystal
structure of a half metallocene compound with the formula 10
according to the present invention, obtained by using a single
crystal X-ray diffractometer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0032] The present invention will now be explained in detail.
[0033] The present invention provides a half metallocene catalyst
satisfying the above formula 1, 2 or 3 and a process for preparing
styrene polymer using the metallocene catalyst as a main
catalyst.
[0034] The metallocene catalyst of the present invention satisfying
the above formula 1, 2 or 3 is a half metallocene compound in which
a cycloalkandienyl group and a amine-based ligand are coordinated
by a transition metal (central metal) of Groups 3 to 10 in the
periodic table. The amine-based ligand has a plurality of binding
sites and high steric hinderance and includes triethanolamine,
N-alkylethanolamine and N-dialkylethanolamine. Therefore, since
each central metal (transition metal) makes cationic polymerization
active species during polymerization and the cationic
polymerization ion active species are stabilized by the ligand
having a plurality of binding sites, that is, the active species
produced at a high temperature during the polymerization become
stable by the ligand, it is expected that the metallocene catalyst
according to the present invention exhibits much higher activity at
a high polymerization temperature as compared to the conventional
catalyst. Accordingly, it is further expected that the half
metallocene catalyst of the present invention makes molecular
weight control of polymers easy as well as is possible to produce
styrene polymer having high polymerization activity, superior
stereoregularity and high melting point even at a high
polymerization temperature and at low cocatalyst to catalyst
ratio.
[0035] The half metallocene catalyst of the formula 1, 2 and 3,
having a ligand with a plurality of binding sites and high steric
hinderance, such as triethanolamine, N-alkylethanolamine and
N-dialkylethanolamine, can be prepared by i) preparing an alkali
metal salt of a cycloalkandienyl ligand, ii) reacting the alkali
metal salt with a transition metal compound having a leaving group
which can be easily removed for substitution and then iii) reacting
the transition metal with any of triethanolamine,
N-alkyldiethanolamine and N-dialkylethanol ligand.
[0036] Alternatively, the half metallocene catalyst can be prepared
by i) reacting a transition metal compound having a leaving group
being easily separable for substitution with a triethanolamine,
N-alkylethanolamine or N-dialkylethanolamine ligand, and then ii)
reacting the transition metal compound of i) with an alkali metal
salt of a cycloalkanedienyl group
[0037] In a process for preparation of the metallocene catalyst
above, the alkali metal salt of a cycloalkandienyl group includes
lithium salt, sodium salt, and potassium salt. These salts can be
prepared by reacing a ligand having a cycloalkanedienyl structure
with n-butyllithium, sec-butyllithium, tert-butyllithium,
methyllithium, sodium methoxide, sodium ethoxide, potassium
tert-butoxide, potassium hydroxide, methylmagnesium chloride,
ethylmagnesium bromide, dimethylmagnesium, lithium, sodium,
potassium, etc. The cycloalkanedienyl alkali metal salt prepared by
the reactions above include cyclopentadienyl lithium,
cyclopentadienyl sodium, cyclopentadienyl potassium,
cyclopentadienyl magnesium, methylcyclopenta dienyl lithium,
methylcyclopentadienyl sodium, methylcyclopentadienyl potassium,
tetramethylcyclopentadienyl lithium, tetramethylcyclopentadienyl
sodium, tetramethylcyclopentadienyl potassium, indenyl lithium,
indenyl sodium, indenyl potassium, fluorenyl lithium, etc.
[0038] The transition metal compound having a leaving group which
is a ligand easily separable for substitution includes titanium
tetrachloride, titanium tetrachloride ditetrahydrofuran, zirconium
tetrachloride, hafnium tetrachloride, vanadium tetrachloride,
titanium tetraiodide, titanium tetrabromide, titanium
tetrafluoride, vanadium oxide trichloride, titanium
tetraisopropoxide, chlorotitanium triisopropoxide, dichlorotitanium
diisopropoxide, trichlorotitanium momoisopropoxide, chlorotitanium
triphenoxide, chlorotitanium tributoxide, chlorotitanium
triethoxide, etc.
[0039] The half metallocene compound includes
cyclopentadienyltitanium trichloride,
cyclopentadienylmethoxytitanium dichloride,
cyclopentadienylmethoxytitanium monochloride,
cyclopentadienyltitanium trimethoxide,
methylcyclopentadienyltitanium trichloride,
methylcyclopentadienylmethoxytitaium dichloride,
methylcyclopentadienylmethoxytitaium monochloride,
methylcyclopentadienyltitanium trimethoxide,
pentamethylcyclopentadienyl titanium trichloride,
pentamethylcyclopentadienylmethoxytitanium dichloride,
pentamethylcyclopentadienylmethoxy titanium monochloride,
pentamethylcyclopentadienyltitanium trimethoxide, indenyltitanium
trichloride, indenylmethoxytitanium dichloride,
indenyldimethoxytitanium monochloride, and indenyltitanium
trimetoxide.
[0040] The ligand having a plurality of binding sites and high
steric hinderance, such as triethanolamine, N-alkylethanolamine and
N-dialkylethanolamine, can be prepared by reacting ethanolamine
with epoxide.
[0041] In the ligand compound of triethanolamine,
N-alkyldiethanolamine or N-dialkylethanolamine compound, a
substitution group giving steric hinderance (E.sup.1 to E.sup.3 in
the formulas 1 to 3) may be C.sub.1-20 cycloalkyl group, alkylsilyl
group, C.sub.6-20 aryl group, arylalkyl group or alkylaryl group
where the alkyl component may be a straight structure or a branch
structure. The examples of the ligand compound include
2-dialkyl-2-hydroxyethylamine, 3-dialkyl-3-hydroxypropylamine,
4-dialkyl-4-hydroxybutylamine, 5-dialkyl-5-hydroxypentylamine,
6-dialkyl-6-hydroxyhexylamine,
N,N-bis(2-dialkyl-2-hydroxyethyl)amine,
N,N-bis(3-dialkyl-3-hydroxypropyl)amine,
N,N-bis(4-dialkyl-4-hydroxybutyl)amine,
N,N-bis(5-dialkyl-5-hydroxypentyl)amine,
N,N-bis(6-dialkyl-6-hydroxyhexyl)amine, N,N,N-tris
(2-dialkyl-2-hydroxyethyl)amine, N,N,N-tris
(3-dialkyl-3-hydroxypropyl)amine,
N,N,N-tris(4-dialkyl-4-hydroxybutyl)amine, N,N,N-tris
(5-dialkyl-5-hydroxypentyl)amine,
N,N,N-tris(6-dialkyl-6-hydroxyhexyl)amine, etc. These are
alcholamine compounds, each containing one or more sterically
limited hydroxyl alkyl group bounded to a nitrogen atom of an amine
group. The examples of the ligand compound further include
(2-dialkyl-2-hydroxyethyl) -2-hydroxyethylamine,
(3-dialkyl-3-hydroxypropyl)-3-hydroxypropylamine,
(4-dialkyl-4-hydroxybutyl)-4-hydroxybutylamine,
(5-dialkyl-5-hydroxypentyl)-5-hydroxypentylamine,
(6-dialkyl-6-hydroxyhexyl)-6-hydroxyhexylamine,
(2-dialkyl-2-hydroxyethyl)-bis(2-hydroxyethyl)amine,
(3-dialkyl-3-hydroxypropyl)-bis(3-hydroxypropyl)amine,
(4-dialkyl-4-hydroxybutyl)-bis(4-hydroxybutyl)amine,
(5-dialkyl-5-hydroxypentyl)-bis(5-hydroxypentyl)amine,
(6-dialkyl-6-hydroxyhexyl)-bis(6-hydroxyhexyl)amine, etc. These are
alcoholamine compounds, each necessarily containing one or more
alcohol group with a sterically limited substitution group and also
having an alcohol group without a sterically limited substitution
group.
[0042] Further, M.sup.1 to M.sup.3 are preferably a Group 4
transition metal on the periodic table, and more preferably
titanium, zirconium or hafnium.
[0043] The ligand having a cycloalkandienyl backbone includes
cyclopentadienyl group, indenyl group, fluorenyl group,
4,5,6,7-tetrahydroindenyl group, 2,3,4,5,6,7,8,9-octahydrofluorenyl
group, etc.
[0044] The halogen group includes fluoro group, chloro group, bromo
group and iodine group.
[0045] The C.sub.1-20 alkyl, C.sub.3-20 cycloalkyl, C.sub.2-20
alkenyl, alkylsillyl, haloalkyl, alkoxy, alkylsilloxy, amino,
alkoxyalkyl, thioalkoxyalkyl, alkylsilloxyalkyl, aminoalkyl, and
alkylphosphinoalkyl groups preferably are methyl, ethyl, propyl,
butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, allyl, 2-butenyl, 2-pentenyl, methylsillyl,
dimethylsillyl, trimethylsillyl, ethylsillyl, dietylsillyl,
triethylsillyl, propylsillyl, dipropylsillyl, tripropylsillyl,
butylsillyl, di-butylsillyl, tri-butylsillyl, butyldimethylsillyl,
trifluoromethyl, methoxy, ethoxy, propoxy, butoxy, pentoxy,
hexyloxy, methylsiloxy, dimethylsiloxy, trimethylsiloxy,
ethylsiloxy, dietylsiloxy, triethylsiloxy, butyldimethylsiloxy,
dimethylamino, diethylamino, dipropylamino, dibutylamino,
pyrrolidine, piperidine, methoxyethyl, methoxypropyl, methoxybutyl,
thiomethoxyethyl, thiomethoxybutyl, trimethylsilloxyethyl,
dimethylaminoethyl, diethylphosphinobutyl groups, etc.
[0046] The C.sub.6-40 aryl, arylalkyl, alkylaryl, arylsilyl,
arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl,
aryloxoaryl, arylsilloxy, arylalkylsilloxy, arylsilloxoalkyl,
arylsilloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl, and
arylphosphinoalkyl groups preferably are phenyl, biphenyl,
terphenyl, naphtyl, fluorenyl, benzyl, phenylethyl, phenylpropyl,
tolyl, xylyl, butylphenyl, phenylsilyl, phenyldimethylsilyl,
diphenylmethylsilyl, triphenylsilyl, chlorophenyl,
pentafluorophenyl, phenoxy, naphthoxy, phenoxyethyl,
biphenoxybutyl, thiophenoxyethyl, phenoxyphenyl, naphthoxyphenyl,
phenylsiloxy, triphenylsiloxy, phenyldimethylsiloxy,
triphenylsilloxethyl, diphenylsilloxphenyl, aniline, toluidine,
benzylamino, phenylaminoethyl, phenylmethylaminophenyl, and
diethylphosphinobutyl groups, etc.
[0047] Syndiotactic styrene polymer and styrene copolymer with
various physical properties can be obtained using the half
metallocene catalyst represented by the above formula 1, 2 or 3 as
a main catalyst together with a cocatalyst in a styrene
homopolymerization or copolymerization with olefin.
[0048] The cocatalyst used together with the half metallocene
catalyst includes alkylaluminoxane having a repeating unit of the
following formula 18 and week coordinate Lewis acid, and they are
typically used together with alkylaluminum of the following formula
19.
[0049] The compound of the formula 18 may be linear, circular or
network structure, and specifically, the examples thereof include
methylaluminoxane, modified methylaluminoxane, ethylaluminoxane,
butylaluminoxane, hexylaluminoxane, decylaluminoxane, etc.
[0050] The compound of the formula 19 includes trimethylaluminum,
dimethylaluminum chloride, dimethylaluminum methoxide,
methylaluminum dichloride, triethylaluminum, diethylaluminum
chloride, diethylaluminum methoxide, ethylaluminum dichloride,
tri-n-propylaluminum, di-n-propylaluminum chloride,
n-propylaluminum chloride, triisopropylaluminum,
tri-n-butylaluminum, tri-isobutylaluminum, di-isobutylaluminum
hydride, etc.
[0051] The weak coordinate Lewis acid cocatalyst may be ionic or
neutral type, and specifically, the examples include
trimethylammonium tetraphenylborate, tributylammonium
tetraphenylborate, trimethylammonium
tetrakis(pentafluorophenyl)borate, tetramethylammonium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetraphenylborate, dimethylanilinium
tetrakis(pentafluorophenyl)borate, pyridinium tetraphenylborate,
pyridinium tetrakis(pentafluorophenyl)borate, silver
tetrakis(pentafluorophenyl)borate, ferro-cerium
tetrakis(pentafluoropehnyl)borate, triphenylcarbenium
tetrakis(pentafluorophenyl) borate, triphenylcarbenium
tetrakis(3,5-bis(trifluoromethyl)phenyl) borate, sodium
tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tris(pentafluorophenyl)borane,
tris(2,3,4,5-tetrafluorophenyl)borane,
tris(3,5-bis(trifluoromethyl)phenyl)borane,
tris(2,4,6-trifluorophenyl)borane, etc.
[0052] In styrene polymerization or copolymerization with olefin
using the metallocene catalyst, the amount of the cocatalyst used
together is not specifically limited but may vary according to the
kinds.
[0053] The mole ratio of alkylaluminoxane and metallocene catalyst
is in the range of from 1:1 to 106:1, and preferably from 10:1 to
104:1. The mole ratio of alkylaluminum that can be used together
with alkylaluminoxane, and metallocene catalyst is in the range of
from 1:1 to 104:1.
[0054] The mole ratio of week coordinate Lewis acid and metallocene
catalyst is in the range of from 0.1:1 to 50:1, and the mole ratio
of alkylaluminum and metallocene catalyst is in the range of from
1:1 to 3000:1, and preferably from 50:1 to 1000:1.
[0055] The above described metallocene catalyst compounds can be
supported on an inorganic or organic compound for use. A carrier
material or a support material for supporting the metallocene
compound thereon is not limited specifically but may be an
inorganic compound with a large surface area and micropores on the
surface thereof. The examples include silica, alumina, magnesium
chloride (MgCl.sub.2), bauxite, zeolite, CaCl.sub.2, MgO, ZrO2,
TiO2, B.sub.2O.sub.3, CaO, ZnO, BaO and ThO.sub.2. Also,
combinations of these inorganic support materials may be used, for
example, SiO.sub.2--MgO, SiO.sub.2--Al.sub.2O.sub.3,
SiO.sub.2--TiO.sub.2, SiO.sub.2--V.sub.2O.sub.5,
SiO.sub.2--CrO.sub.2O.sub.3, and SiO.sub.2--TiO.sub.2--MgO. The
compounds above can contain a small amount of carbonate, sulfate or
nitrate. Further, organic compounds including starch, cyclodextrin
and polymer can also be used as the support material.
[0056] The monomers that can be polymerized with the catalyst
system of the present invention include styrene, styrene
derivatives, and olefin. Among them, styrene or a styrene
derivative can be homopolymerized, respectively. Further, styrene
and styrene derivatives can be compolymerized. Still further,
styrene or styrene derivatives can be copolymerized with
olefins.
[0057] The styrene derivatives have substituents on a benzene ring,
and the substituents include halogen, C.sub.1-10 alkyl, alkoxy,
ester, thioalkoxy, sillyl, tin, amine, phosphine, halogenated
alkyl, C.sub.2-20 vinyl, aryl, vinylaryl, alkylaryl, aryl alkyl
group, etc. Examples thereof include chlorostyrene, bromostyrene,
fluorostyrene, p-methylstyrene, m-methylstyrene, ethylstyrene,
n-butylstyrene, p-t-butylstyrene, dimethylstyrene, methoxystyrene,
ethoxystyrene, butoxystyrene, methyl-4-styrenylester,
thiomethoxystyrene, trimethylsillylstyrene, triethylsillylstyrene,
t-butyldimethylsillylstyrene, trimethyltin styrene,
dimethylaminostyrene, trimethylphosphinostyrene,
chloromethylstyrene, bromomethylstyrene, 4-vinylbiphenyl,
p-divinylbenzene, m-divinylbenzene, trivinylbenzene,
4,4'-divinylbiphenyl, vinylnaphthalene, etc.
[0058] The olefins that can be used in copolymerization with
styrene or styrene derivatives include C.sub.2-20 olefin,
C.sub.3-20 cycloolefin or cyclodiolefin, C.sub.4-20 diolef in,
etc., and examples thereof include ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 1-octene, 1-decene, cyclopentene, cyclohexene,
cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbonene,
1,3-butadiene, 1,4-pentadiene, 2-methyl-1,3-butadiene,
1,5-hexadiene, etc.
[0059] Polymerization using the catalyst system of the present
invention can be conducted in slurry phase, liquid phase, gas phase
or massive phase. When polymerization is conducted in slurry phase
or liquid phase, solvent can be used as a polymerization medium,
and example solvent include C.sub.4-20 alkane or cycloalkane such
as butane, pentane, hexane, heptane, octane, decane, dodecane,
cyclopentane, methylcyclopentane, cyclohexane, etc.; C.sub.6-20
aromatic arene such as benzene, toluene, xylene, mesitylene, etc.;
and C.sub.1-20 halogen alkane or halogen arene such as
dichloromethane, chloromethane, chloroform, tetrachloromethane,
chloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane,
chlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, etc.
Mixtures of these solvents with a predetermined mixing ratio can be
also used as the solvent. Polymerization in gas phase can be
conducted when an inner pressure of a reactor is in the range of
from 0.01 to 20atm under solvent-free condition.
[0060] Polymerization temperature is -80 to 200.degree. C., and
preferably 0 to 150.degree. C., and polymerization pressure is
suitably 1 to 1000 atm including the pressure of comonomers for
styrene homopolymerization or copolymerization with olefin.
[0061] According to the present invention, polymer can be prepared
by i) introducing a solvent and monomers or monomers only into a
reactor, elevating a temperature of the reactor, and then
introducing alkylaluminum, cocatalyst and main catalyst metallocene
compound into the reactor in this order, or ii) activating a main
catalyst with alkylaluminum and cocatalyst, and then introducing
the activated main catalyst into a reactor containing monomers, or
iii) adding alkylaluminum to monomers before the monomers are
introduced into a reactor, and then introducing a main catalyst
activated with a cocatalyst to the reactor. And, the activation by
bringing a main catalyst into contact with a cocatalyst is
conducted at 0 to 150.degree. C. for 0.1 to 240 minutes and
preferably conducted for 0.1 to 60 minutes.
[0062] The amount of the main catalyst metallocene compound is not
specifically limited, but is suitably 10.sup.-8 to 1.0 M on the
basis of concentration of central metal in reaction system, and
ideally 10.sup.-7 to 10.sup.-2 M.
[0063] Syndiotactic styrene polymers and copolymers obtained by
polymerization using the catalyst system of the present invention
can be controlled in a molecular weight range of 1000 to 10,000,000
and in a molecular weight distribution range of from 1.1 to 100 by
controlling the kinds and the amounts of a main catalyst and a
cocatalyst, reaction temperature, reaction pressure and
concentration of monomers.
[0064] Hereinafter, the present invention will be described in more
detail through examples and comparative examples. Embodiments are
presented on the exemplary purpose but can not be construed to
limit the scope of the present invention.
EXAMPLES
Example 1
Synthesis of Cp*Ti(OCMe.sub.2CH.sub.2).sub.3N(catalyst 1)
Preparation of (HOCMe.sub.2CH.sub.2).sub.3N
[0065] 10 ml (20 mmol) of ammonia (NH.sub.3, 2M solution in MeOH),
4.76 g (66 mmol) of isobutylene oxide and a stirring bar are put
into a 20 ml screw capped vial, and then mixed in the vial at room
temperature for 12 hours to obtain a colorless viscous solution.
Then, the colorless viscous solution in the vial is transferred to
a 250 ml flask and a washing solution obtained by washing the vials
with 20 ml of acetone three times is added to the colorless viscous
solution in the 250 ml flask. Solvent in the solution of the flask
are removed in a rotary evaporator, and then the contents in the
flask are dissolved in a small amount of hexane. The obtained
hexane solution is maintained in a freezer, thereby to obtain
colorless solid. The colorless solid is filtered and then dried
under the vacuum condition. As a result, 4.6 g (yield 98%) of a
white solid, (HOCMe.sub.2CH.sub.2).sub.3N, is obtained and its
.sup.1H NMR result is as follows:
[0066] .sup.1H NMR (300.13 MHZ, CDCl.sub.3, ppm): .delta.=2.55(s,
6H, CH.sub.2), 1.16 (s, 18H, CMe.sub.2). .sup.13C{.sup.1H}NMR (75.4
MHz, CDCl.sub.3, ppm): .delta.=69.92(OCMe2), 61.02(CH.sub.2N),
27.40(OCMe.sub.2)
Preparation of Cp*Ti(OCMe.sub.2CH.sub.2).sub.3N (Catalyst 1)
[0067] 2 mmol (0.47 g) of HOCMe.sub.2CH.sub.2).sub.3N which is
synthesized according to the example 1 process described above is
put into a Schlenk flask and dissolved in 30 ml of toluene. Then, 6
mmol (0.84 ml) of triethylamine is introduced into the Schlenk
flask, and the contents in the flask are mixed together, thereby
obtaining a colorless clear solution. A temperature of the
colorless solution is lowered to -78.degree. C. On the other hand,
2 mmol (0.578 g) of Cp*TiCl.sub.3 is dissolved in 30 ml of toluene
in a different Schlenk flask, thereby obtaining a separate
solution. The separate solution is gradually added to the colorless
clear solution drop by drop. After all the toluene solution is
added to the colorless clear solution, a temperature of the
solution mixture is slowly raised to a room temperature, and the
solution mixture in the Schlenk flask is agitated overnight. Then,
the solution mixture is filtered using a celite filter to separate
ammonium salt therefrom, thereby obtaining a yellow clear solution.
Solvent in the yellow clear solution is removed under the vacuum
condition, and the resultant material after the solvent removal is
dried for a long time. As a result, 0.8 g (yield 97%) of yellowish
orange solid, catalyst 1 of the formula 9, is obtained and its
.sup.1H NMR result is as follows:
[0068] .sup.1H NMR (300.13 MHz, CDCl.sub.3, ppm): .delta.=3.16(dd,
J.sub.1/2=6.6 Hz, J.sub.1/3=11.9 Hz, 3H, CH.sub.2), 2.81(dd,
J.sub.1/2=7.4 Hz, J.sub.1/3=11.9 Hz, 3H, CH.sub.2). 1.96 (s, 15H,
C.sub.5Me.sub.5), 1.20 (s, 9H, CMe.sub.2), 1.11 (s, 9H, CMe.sub.2).
.sup.13C {.sup.1H} NMR (75.4 MHz, CDCl.sub.3, ppm):
.delta.=125.7(C.sub.5Me.sub.5), 84.34(OCMe.sub.2) 61.35(CH.sub.2N),
31.17(OCMe.sub.2) 29.30(OCMe.sub.2), 11.95(C.sub.5Me.sub.5).
EI-MS:m/z=414. ##STR6##
Example 2
Synthesis of Cp*Ti(OCMe.sub.2CH.sub.2).sub.2N(CH.sub.2CH.sub.2O)
(catalyst 2)
Preparation of (HOCMe.sub.2) .sub.2N (CH.sub.2CH.sub.2OH)
[0069] 3.05 g (50 mmol) of ethanolamine, 7.93 g (110 mmol) of
isobutylene oxide and a stirring bar are put into a screw capped
vial of 20 ml, and mixed together at a room temperature for 12
hours to obtain a colorless viscous solution. The colorless viscous
solution is transferred to a 250 ml flask and a washing solution
obtained by washing the vial with 20 ml of acetone three times is
added to the colorless viscous solution. Solvent in the colorless
solution is removed in a rotary evaporator and then the resultant
material after the solvent evaporation is dried under the vacuum
condition for a long time. As a result, log (yield 97%) of
waterwhite oil (HOCMe.sub.2CH.sub.2).sub.2N(CH.sub.2CH.sub.2OH) is
obtained, and its .sup.1H NMR result is as follows:
[0070] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=3.60(t,
J=5.4 Hz, 2H, CH.sub.2CH.sub.2N), 2.77(t, J=5.4 Hz, 2H,
CH.sub.2CH.sub.2N), 2.53 (s, 4H, CMe.sub.2CH.sub.2N), 1.17(s, 12H,
CMe.sub.2). .sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=71.03(OCH.sub.2), 68.81(OCMe.sub.2), 61.39(NCH.sub.2),
60.49(NCH.sub.2), 28.21(OCMe.sub.2).
Preparation of Cp*Ti(OCM.sub.2CH.sub.2).sub.2N(CH.sub.2CH.sub.2O)
(catalyst 2)
[0071] 1.45 mmol (0.298 g) of
(HOCMe.sub.2CH.sub.2).sub.2N(CH.sub.2CH.sub.2OH) which is
synthesized according to the example 2 process described above is
put into a Schlenk flask and dissolved in 30 ml of toluene. Then,
4.8 mmol (0.7 ml) of triethylamine is introduced into the Schlenk
flask, and the contents in the flask are mixed together to obtain a
colorless clean solution. The temperature of the colorless clear
solution is lowered to -78.degree. C. On the other hand, 1.45 mmol
(0.42 g) of Cp*TiCl.sub.3 is dissolved in 30 ml of toluene in a
different Schlenk flask, thereby obtaining a separate solution. The
separate solution is gradually added to the colorless clear
solution drop by drop. After all the separate solution is added to
the colorless clear solution, a temperature of the solution mixture
in the Schlenk flask is raised to a room temperature, and the
solution mixture is agitated overnight. Then, the solution mixture
is filtered using a celite filter to separate ammonium salt
therefrom, thereby obtaining a yellow clear solution. Solvent in
the yellow clear solution is removed under the vacuum condition,
and the resultant material after the solvent removal of the yellow
clear solution is dried for a long time. As a result, 0.56 g (yield
100%) of yellow solid, catalyst 2 of the formula 10, is obtained,
and its .sup.1H NMR result is as follows: Further, the structure of
this catalyst is analyzed by an X-ray diffraction apparatus and its
result is shown in FIG. 1.
[0072] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.10(t,
J=5.5 Hz, 2H, CH.sub.2CH.sub.2N), 2.94-2.80(m, 6H,
CH.sub.2CH.sub.2N and CMe.sub.2CH.sub.2N), 1.85(s, 15H,
C.sub.5Me.sub.5), 0.90(d, J=7.4 Hz, 12H, CMe.sub.2),
.sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=121.4(C.sub.5Me.sub.5), 81.29(OCH.sub.2), 70.91(OCMe.sub.2)
70.50(NCH.sub.2), 63.35(NCH.sub.2), 31.79(OcMe.sub.2),
31.14(OCMe.sub.2), 11.13(C.sub.5Me.sub.5), EI-MS: m/z=385.
##STR7##
Example 3
Synthesis of Cp*Ti(OCMe.sub.2CH.sub.2).sub.2N(CH.sub.2CH.sub.2O)
(catalyst 3)
Preparation of (HOCMe.sub.2CH.sub.2)N(CH.sub.2CH.sub.2OH).sub.2
[0073] 5.26 g (50 mmol) of diethanolamine, 3.61 g (55 mmol) of
isobutylene oxide and a stirring bar are put into a 20 ml screw
capped vial, and mixed together at a room temperature for 12 hours
to obtain a colorless viscous solution. The colorless viscous
solution is transferred to a 250 ml flask and a washing solution
obtained by washing the vial with acetone three times is added to
the colorless viscous solution. Solvent in the colorless viscous
solution are removed in a rotary evaporator, and then the resultant
material after the solvent evaporation is dried under the vacuum
condition for a long time. As a result, 8.6 g (yield 97%) of
waterwhite oil (HOCMe.sub.2CH.sub.2)N(CH.sub.2CH.sub.2OH).sub.2 is
obtained, and its .sup.1H NMR result is as follows:
[0074] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.62(br
s, 3H, OH) 3.58(t, J=4.7 Hz, 4H, CH.sub.2CH.sub.2N), 2.65(t, J=4.7
Hz, 2H, CH.sub.2CH.sub.2N), 2.42 (s, 2H, CMe.sub.2CH.sub.2N),
1.15(s, 6H, CMe.sub.2). .sup.13C{.sup.1H} NMR (75.47 MHz,
CDCl.sub.3, ppm): .delta.=70.73(OCH.sub.2), 66.85(OCMe.sub.2)
59.94(NCH.sub.2), 59.21(NCH.sub.2), 27.73(OCMe.sub.2).
Preparation of Cp*Ti(OCM.sub.2CH.sub.2)N(CH.sub.2CH.sub.2O).sub.2
(catalyst 3)
[0075] 1.45 mmol (0.257 g) of
(HOCMe.sub.2CH.sub.2)N(CH.sub.2CH.sub.2OH).sub.2 which is
synthesized according to the example 3 process described above is
put into a Schlenk flask and dissolved in 30 ml of toluene. Then,
4.8 mmol (0.7 ml) of triethylamine is introduced into the Schlenk
flask, and the contents in the flask are mixed together, thereby
obtaining a colorless clear solution. The temperature of the
colorless clear solution is lowered to -78.degree. C. On the other
hand, 1.45 mmol (0.42 g) of Cp*TiCl.sub.3 is dissolved in 30 ml of
toluene in a different Schlenk flask, thereby obtaining a separate
solution. The separate solution is gradually added to the colorless
clea solution drop by drop. After all the separate solution is
dropped to the colorless solution, a temperature of the solution
mixture in the Schlenk flask is raised to a room temperature, and
the solution mixture is further agitated overnight. Next day, the
solution mixture is filtered using a celite filter to separate
ammonium salt therefrom, thereby obtaining a yellow clear solution.
Solvent in the yellow clear solution is removed under vacuum, and
the resultant material after the removal of solvent from the yellow
clear solution is dried for a long time. As a result, 0.51 g (yield
98%) of yellow solid, catalyst 3 of the following formula 11 is
obtained, and its .sup.1H NMR result is as follows:
[0076] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.17(t,
J=5.4 Hz, 4H, CH.sub.2CH.sub.2N), 2.93-2.85(m, 6H,
CH.sub.2CH.sub.2N and CMe.sub.2CH.sub.2N), 1.86(s, 15H,
C.sub.5Me.sub.5), 0.90(s, 6H, CMe.sub.2). .sup.13C{(H} NMR (75.47
MHz, CDCl.sub.3, ppm): .delta.=121.9(C.sub.5Me.sub.5),
81.94(OCH.sub.2), 70.70(OCMe.sub.2), 67.46(NCH.sub.2), 59.56
(NCH.sub.2), 32.13 (OCMe.sub.2), 11.07 (C.sub.5Me.sub.5), EI-MS:
m/z=357. ##STR8##
Example 4
Synthesis of Cp*Ti(OPh)3N(catalyst 4)
[0077] 2 mmol (0.59 g) of tris(2-hydroxyphenyl)amine is dissolved
in a toluene in a Schlenk flask. Then, 6 mmol(0.84 ml) of
triethylamine is added to the tris(2-hydroxyphenyl)amine-toluene
solution, thereby obtaining a colorless clear solution. The
temperature of the colorless clear solution is lowered to
-78.degree. C. Then, 2 mmol(0.578 g) of Cp*TiCl.sub.3 is dissolved
in 30 ml of toluene in a different Schlenk flask, thereby obtaining
a solution. This solution is gradually added to the colorless clear
solution drop by drop. After all the solution is dropped to the
colorless clear solution, a temperature of the solution mixture is
raised to a room temperature and then the solution mixture is
agitated overnight. Next, the solution mixture is filtered using a
celite filter to separate ammonium salt therefrom, thereby
obtaining a yellow clear solution. Solvent in the yellow clear
solution is removed under vacuum, and the resultant material after
the removal of solvent from the yellow clear solution is dried for
a long time. As a result, 0.49 g (yield 52%) of orange-yellow
solid, catalyst 4 of the following formula 12 is obtained, and its
.sup.1H NMR result is as follows:
[0078] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=7.43(d,
J=7.9 Hz, 3H, Ph-H), 7.04(t, J=8.0 Hz, 3H, Ph-H), 6.69(t, J=7.9 Hz,
3H, Ph-H), 6.51(d, J=8.0 Hz, 3H, Ph-H), 2.15 (s, 15H,
C.sub.5Me.sub.5). .sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3,
ppm): .delta.=164.0(Ph), 1(Ph), 128.9(Ph), 128.5(Ph),
126.0(C.sub.5Me.sub.5), 119.2(Ph), 116.6(Ph),
11.56(C.sub.5Me.sub.5). EI-MS: m/z=473. ##STR9##
Example 5
Synthesis of Cp*TiCl{(OCMe.sub.2CH.sub.2).sub.2NMe} (catalyst5)
Preparation of (HOCMe.sub.2 CH.sub.2).sub.2NMe
[0079] 25 ml (50 mmol) of methylamine (2M solution in MeOH), 7.93
g(110 mmol) of isobutylene oxide and a stirring bar are put into a
20 ml screw capped vial and mixed together at 50.degree. C. for 12
hours, thereby obtaining a colorless viscous material. A
temperature of the colorless viscous material is lowered to a room
temperature, and then the colorless viscous material is transferred
to a 250 ml flask. Than, a washing solution obtained by washing the
vial with 20 ml of acetone three times is added to the contents in
the same flask. Solvent in the contents in the flask is removed in
a rotary evaporator and then the resultant material after the
removal of the solvent is dried under vacuum for a long time to
obtain 8.7 g(yield 99%) of waterwhite oil,
(OHCMe.sub.2CH.sub.2).sub.2NMe, and its .sup.1H NMR result is as
follows:
[0080] .sup.1H NMR (300. 13 MHz, CDCl.sub.3, ppm): .delta.=3.86(s,
2H, OH), 2.46(s, 4H, CMe.sub.2 CH.sub.2N), 2.42(s, 3H, NMe),
1.10(s, 12H, CMe.sub.2). .sup.13C {.sup.1H} NMR (75.47 MHz,
CDCl.sub.3, ppm): .delta.=72.05(OCMe.sub.2), 71.48(OCMe.sub.2),
61.39(NCH.sub.2), 60.49 (NMe), 28.21(OCMe.sub.2).
Preparation of Cp*TiCl{(OCMe.sub.2CH.sub.2).sub.2NMe} (catalyst
5)
[0081] 2.42 ml (0.424 g) of (HOCMe.sub.2CH.sub.2).sub.2NMe which is
synthesized according to the example 5 process described above is
transferred to a Schlenk flask and dissolved in 30 ml of toluene.
Then, 5 mmol(0.81 ml) of triethylamine is added to the solution in
the Schlenk flask, thereby obtaining an colorless clear solution. A
temperature of the colorless clear solution is lowered to
-78.degree. C. On the other hand, 2.42 mmol(0.7 g) of Cp*TiCl.sub.3
is dissolved in 30 ml of toluene in a different Schlenk flask to
obtain a separate solution. This separately prepared solution is
gradually added to the colorless clear solution drop by drop. After
all the separately prepared solution is added to the colorless
clear solution, the temperature of the solution mixture is raised
to a room temperature and the solution mixture is agitated
overnight. Next day, the solution mixture is filtered using a celie
filter to separate ammonium salt therefrom, thereby obtaining a
yellow clear solution. The solvent in the yellow clear solution is
removed under vacuum, and the resultant material after the removal
of the solvent is dried for a long time, so that 0.85 g (yield 89%)
of yellow solid, catalyst 5 of the following formula 13 is obtained
and its .sup.1H NMR result is as follows:
[0082] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=2.67(q,
J=11.6 Hz, 4H, CH.sub.2N), 2.58(s, 3H, NMe), 2.04(s, 15H,
CsMe.sub.5), 1.18(d, J=4.4 Hz, 12H, CMe.sub.2). .sup.13C{.sup.1H}
NMR (75.47 MHz, CDCl.sub.3, ppm): .delta.=125.1(C.sub.5Me.sub.5),
88.13(OCMe.sub.2), 73.68(NCH.sub.2), 50.29(NMe), 28.59(OCMe.sub.2),
12.17 (C.sub.5Me.sub.5). EI-MS: m/z=393. ##STR10##
Example 6
Synthesis of Cp*Ti(OMe){(OCMe.sub.2CH.sub.2).sub.2NMe} (catalyst
6)
[0083] 2.42 mmol (0.424 g) of a ligand (HOCMe.sub.2).sub.2NMe
synthesized according to the example 5 process is transferred to a
Shlenk flask and dissolved in 30 ml of toluene in the flask. A
temperature of the solution in the flask is lowered to -78.degree.
C. Then, a separate solution is prepared by dissolving 2.42 mmol
(0.67 g) of Cp*Ti(OMe).sub.3 in 30 ml of toluene. The separate
solution is gradually added to the ligand solution in the flask
drop by drop. After all the solution is added to the ligand
solution, the temperature of the solution mixture is gradually
raised to a room temperature, and agitated overnight. Next, the
solvent in the solution mixture is removed under the vacuum
condition and the resultant material after the removal of the
solvent is dried for a long time. As a result, 0.83 g (yield 92%)
of yellow solid, catalyst 6 of the following formula 14 is
obtained, and its .sup.1H NMR result is as follows:
[0084] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.01(s,
3H, OMe), 2.73(q, J=12.0 Hz, 4H, CH.sub.2N), 2.61(s, 3H, NMe),
2.01(s, 15H, C.sub.5Me.sub.5), 1.21(d, J=5.2 Hz, 12H, CMe.sub.2).
.sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=125.9(C.sub.5Me.sub.5), 87.44(OCMe.sub.2), 75.15(NCH.sub.2)
62.32(OMe), 51.33(NMe), 29.43(OCMe.sub.2), 11.29(C.sub.5Me.sub.5).
##STR11##
Example 7
Synthesis of Cp*TiCl{(OCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2O)}
(catalyst 7)
Preparation of (HOCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2OH)
[0085] 7.51 g (100 mmol) of N-methylethanolamine, 7.93 g (110 mmol)
of isobutylene oxide and a stirring bar are put into a 20 ml screw
capped vial and mixed together in the vial at 50.degree. C. for 12
hours, and then a reaction temperature of the reaction mixture is
lowered to a room temperature, thereby obtaining a colorless
viscous solution. The colorless viscous solution is transferred to
a 250 ml flask. On the other hand, a washing solution obtained by
washing the vial with 20 ml of acetone three times is added to the
colorless viscous solution in the flask. All the solvent in the
solution in the flask are removed in a rotary evaporator, and the
resultant material after the removal of solvent is dried under the
vacuum condition for a long time, thereby obtaining 14.3 g (yield
97%) of a waterwhite oil,
(HOCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2OH), and its .sup.1H NMR
result is as follows:
[0086] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=3.56(t,
J=5.4 Hz, 2H, NCH.sub.2CH.sub.2), 3.41(br, s, 2H, OH), 2.60(t,
J=5.5 Hz, 2H, NCH.sub.2CH.sub.2), 2.37(s,3H, NMe), 2.34(s, 2H,
CMe.sub.2CH.sub.2N), 1.12(s, 6H, CMe.sub.2). .sup.13C{.sup.1H} NMR
(75.47 MHz, CDCl.sub.3, ppm): .delta.=70.72(OCH.sub.2)
68.29(OCMe.sub.2), 61.75(NCH.sub.2), 45.46(NMe),
27.62(OCMe.sub.2).
Preparation of Cp*TiCl{(OCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2O)}
(catalyst 7)
[0087] 2.42 mmol (0.356 g) of
(HOCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2OH) which is synthesized
according to the example 7 process described above is put into a
Schlenk flask and dissolved in 30 ml of toluene. Then, 5 mmol (0.8
ml) of triethylamine is introduced into the Schlenk flask, and the
contents in the Schlenk flask are mixed together, thereby obtaining
a colorless clear solution. A temperature of the colorless clear
solution is lowered to -78.degree. C. On the other hand, 2.42 mmol
(0.7 g) of Cp*TiCl.sub.3 is dissolved in 30 ml of toluene in a
different Schlenk flask to obtain a separate solution. The separate
solution is gradually added to the colorless clear solution drop by
drop. After dropping all the separate solution to the colorless
solution, a temperature of the solution mixture in the Schlenk
flask is gradually raised to a room temperature, and the solution
mixture is further agitated overnight. Then, the solution mixture
is filtered using a celite filter to separate ammonium salt
therefrom, thereby obtaining a yellow clear solution. Solvent in
the yellow clear solution is removed under the vacuum condition,
and the resultant material after the removal of solvent is dried
for a long time. As a result, 0.77 g (yield 88%) of yellow solid,
catalyst 7 of the following formula 15 is obtained, and its .sup.1H
NMR result is as follows:
[0088] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm):
.delta.=4.36-4.28(m, 2H, CH.sub.2O), 2.86-2.79 (m, 1H,
CH.sub.2CH.sub.2N), 2.72(d, J=3.3 Hz, 2H, CMe.sub.2CH.sub.2N),
2.70-2.61(m, 1H, CH.sub.2CH.sub.2N), 2.58(s, 3H, NMe), 1.97 (s,
15H, C.sub.5Me.sub.5), 1.22(d, J=10 Hz, 6H, CMe.sub.2).
.sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=125.8(C.sub.5Me.sub.5), 85.95(OCH.sub.2) 72.88(OCMe.sub.2),
68.29(CH.sub.2CH.sub.2N) 61.60(CMe.sub.2CH.sub.2N) 47.79(NMe),
31.92 (OCMe.sub.2), 31.16 (OCMe.sub.2), 12.00 (C.sub.5Mes). EI-MS:
m/z=363. ##STR12##
Example 8
Synthesis of Cp*Ti(OMe){(OCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2O)}
(catalyst 8)
[0089] 2.42 mmol (0.356 g) of the ligand,
(HOCMe.sub.2CH.sub.2)NMe(CH.sub.2CH.sub.2OH), which is synthesized
according to the example 7 process is put into a Schlenk flask and
dissolved in 30 ml of toluene in the Schlenk flask. A temperature
of the ligand and toluene solution is lowered to -78.degree. C.
Then, 2.42 mmol(0.67 g) of Cp*Ti(OMe).sub.3 is dissolved in 30 ml
of toluene in a different Schlenk flask, thereby obtaining a
separate solution. This separate solution is gradually added to the
ligand and toluene solution drop by drop. After all the separate
solution is added to the ligand and tolune solution, a temperature
of the solution mixture is gradually raised to a room temperature
and then the solution mixture is agitated overnight. Then, solvent
in the solution mixture is removed under the vacuum condition, and
the resultant material obtained after the removal of the solvent is
dried for a long time. As a result, 0.76 g (yield 91%) of yellow
solid, catalyst 8 of the following formula 16 is obtained, and its
.sup.1H NMR result is as follows:
[0090] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.25(m,
2H, CH.sub.2O), 4.01 (s, 3H, OMe), 2.77(m, 1H, CH.sub.2CH.sub.2N),
2.65(d, J=3.8 Hz, 2H, CMe.sub.2CH.sub.2N), 2.85(m, 1H,
CH.sub.2CH.sub.2N), 2.51(s, 3H, NMe), 2.01 (s, 15H,
C.sub.5Me.sub.5), 1.19(d, J=9.1 Hz, 6H, CMe.sub.2).
.sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=125.3(C.sub.5Me.sub.5), 84.15(OCH.sub.2), 77.93(OCMe.sub.2)
65.75(CH.sub.2CH.sub.2N) 63.51(OMe), 62.58(CMe.sub.2CH.sub.2N), 48.
94(NMe), 32.88 (OCMe.sub.2), 30.09 (CCMe.sub.2), 11.79
(C.sub.5Me.sub.5). ##STR13##
Example 9
Synthesis of Cp*Ti(OMe).sub.2(OCMe.sub.2CH.sub.2NMe.sub.2)
(catalyst 9)
Preparation of HOCMe.sub.2CH.sub.2NMe.sub.2
[0091] 20 ml(40 mmol) of dimethylamine (HNMe.sub.2, 2M solution in
MeOH), 3.17 g (46 mmol) of isobutylene oxide and a stirring bar are
put into a 20 ml screw capped vial and mixed together in the vial
at a room temperature for 12 hours, thereby obtaining a colorless
viscous solution. The colorless viscous solution is transferred to
a 250 ml flask, and a washing solution obtained by washing the vial
with 20 ml of acetone three times is added to the colorless viscous
solution. Solvent in the colorless viscous solution is removed in a
rotary evaporator, and then the resultant material after the
removal of the solvent is dried under the vacuum condition for a
long time. As a result, 2.6 g (yield 55%) of a waterwhite liquid,
HOCMe.sub.2CH.sub.2NMe.sub.2, is obtained, and its .sup.1H NMR
result is as follows:
[0092] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=3.43(br
s, 1H, OH), 2.33 (s, 6H, NMe.sub.2), 2.24(s, 2H, CH.sub.2N),
1.13(s, 6H, CMe.sub.2). .sup.13C{.sup.1H} NMR (75.47 MHz,
CDCl.sub.3, ppm): .delta.=69.92(OCMe.sub.2), 61.02(CH.sub.2N),
27.40(OCMe.sub.2).
Preparation of Cp*Ti(OMe).sub.2(OCMe.sub.2CH.sub.2NMe.sub.2)
(catalyst 9)
[0093] 2.42 mmol (0.284 g) of HOCMe.sub.2CH.sub.2NMe.sub.2 which is
synthesized according to the example 9 process described above is
put into a first Schlenk flask and dissolved in 30 ml of toluene.
Then, a temperature of the solution in the first Schlenk flask is
lowered to -78.degree. C. On the other hand, 2.42 mmol(0.67 g) of
Cp*Ti(OMe).sub.3 is dissolved in 30 ml of toluene in a second
Schlenk flask to obtain a separate solution. The separate solution
is gradually added to the solution in the first Schlenk flask drop
by drop. After all the separate solution is added to the solution
in the first Schlenk flask, the solution mixture is gradually
raised to a room temperature, and then agitated overnight. Then,
solvent in the solution mixture is removed under the vacuum
condition and the resultant material after the removal of the
solvent is dried for a long time. As a result, 0.64 g (yield 88%)
of yellow solid, catalyst 9 of the following formula 17 is
obtained, and its .sup.1H NMR result is as follows:
[0094] .sup.1H NMR (300, 13 MHz, CDCl.sub.3, ppm): .delta.=4.12(s,
6H, OMe), 2.68(s, 2H, CH.sub.2N), 2.55(s, 6H, NMe.sub.2), 1.98(s,
15H, C.sub.5Me.sub.5), 1.12(d, J=7.8 Hz, 6H, CMe.sub.2).
.sup.13C{.sup.1H} NMR (75.47 MHz, CDCl.sub.3, ppm):
.delta.=124.5(C.sub.5Me.sub.5), 76.34(OCMe.sub.2), 65.29(OMe),
63.75(NMe), 47.36(NMe.sub.2), 34.51(OCMe.sub.2), 11.33
(C.sub.5Me.sub.5). ##STR14##
Example 10
Preparation of Styrene Polymer (in Solution Phase)
[0095] Liquid phase polymerization for producing styrene polymer is
conducted using the half metallocene catalysts according to the
examples 1 to 9. The polymerization process is as follows:
[0096] 70 ml of purified heptane is introduced into a
polymerization reactor filled with highly purified nitrogen and a
temperature of the reactor is raised to 50.degree. C. Then, 30 ml
of styrene, 0.5 ml of tri-isobutyl aluminum (1.0M toluene solution)
and 0.44 ml of methyl-aluminum oxane (2.1M toluene solution,
purchased from Akzo Chemical Co.) are sequentially introduced into
the reactor. While the reaction mixture in the reactor are agitated
vigorously, 0.75 ml of toluene solution (containing 3.75micromoles
of Ti), in which one of the metallocene catalysts above is
dissolved, is added to the reaction mixture in the reactor. After
mixing the all the ingredients in the reactor for 1 hour, 10 wt %
of hydrochloric acid-ethanol solution is introduced into the
reactor to terminate the reaction. Then, the reaction product is
filtered and white precipitate is obtained. The precipitate is
washed with ethanol and dried at 50.degree. C. in a vacuum oven
overnight to obtain styrene polymer. The results of polymerization
conducted using the catalysts according to the examples 1 to 9 of
the present invention and natures of the produced polymers are
shown in Table 1 for each catalyst. The respective polymers are
extracted under reflux of methylethylketone for 12 hours, thereby
obtaining polymers which remain without dissolving during the
extraction. The extracted polymer is analyzed by a carbon nuclear
magnetic resonance (NMR) spectroscopic investigation method, and it
is found that the polymers have the syndiotatic structure.
Comparative Example 1
[0097] In this example, all the process steps and most of the
materials are the same as used in the example 10 except the kinds
of the catalyst. In this example, a conventional catalyst
Cp*Ti(OMe).sub.3 is used. Polymerization results obtained using the
conventional catalyst Cp*Ti(OMe).sub.3 and the nature of the
resultant polymer are shown in Table 1.
Comparative Example 2
[0098] In this example, all the process steps and most of the
materials are the same as used in the example 10 except the
catalyst used. According to this example, a conventional catalyst
Cp*Ti(OCH.sub.2CH.sub.2)N is used. Polymerization results obtained
by using the conventional catalyst Cp*Ti(OCH.sub.2CH.sub.2)N and
the nature of the resultant polymer are shown in Table 1.
Comparative Example 3
[0099] In this example, all the process steps and most of the
materials are the same as used in the example 10 of the present
invention except the catalyst used. According to this example, a
conventional catalyst Cp*Ti(OCHMeCH.sub.2).sub.3N is used.
Polymerization results obtained by using the conventional catalyst
Cp*Ti(OCH.sub.2CH.sub.2).sub.3N and the nature of the resultant
polymer are shown in Table 1. TABLE-US-00001 TABLE 1 Results of
polymerization conducted in solution phase Distribution Activity(kg
Syndiotac- Molecular Of Molecular Melting Temp. Catalyst Yield (g)
PS/molTi hr) ticity (%) Weight (Mw) Weight (Mw/Mn) (.degree. C.) 1
0.16 21 92 415,000 2.2 269 2 9.76 1302 94 575,000 1.9 272 3 3.68
495 92 523,000 1.9 271 4 9.74 1298 93 625,000 2.1 270 5 1.99 265 90
210,000 2.2 268 6 9.84 1313 93 594,000 2.0 268 7 2.15 287 91
176,000 2.9 266 8 9.33 1244 92 418,000 2.8 269 9 9.60 1280 95
467,000 2.0 267 Comparative Example 1 9.30 1240 91 245,000 2.1 269
Cp*Ti(OMe).sub.3 Comparative Example 2 6.05 807 93 314,000 2.3 271
Cp*Ti--(OCH.sub.2CH.sub.2).sub.3N Comparative Example 3 3.14 418 90
287,000 2.2 270 Cp*Ti(OCH-MeCH.sub.2).sub.3N
Example 11
Preparation of Styrene Polymer (in Bulk Phase)
[0100] Polymerization of styrene in mass phase is conducted in the
presence of the half metallocene catalysts according to the
examples 1 to 9 of the present invention.
[0101] 100 ml of purified styrene is introduced into a
polymerization reactor filled with highly purified nitrogen and a
temperature of the reactor is raised to 50.degree. C. Then, 5 ml of
tri-isobutyl aluminum (1.0M toluene solution) and 5 ml of methyl
aluminoxane (2.1M toluene solution, purchased from Akzo Chemical
Co.) are sequentially introduced into the reactor. While the
contents in the reactor are mixed vigorously, 5 ml of toluene
solution (containing 50 micromoles of Ti), in which one of the
metallocene catalysts according to the examples 1 to 9, is
dissolved, is introduced into the reactor. After mixing the
reaction mixture in the reactor for 1 hour, 10 wt % of hydrochloric
acid-ethanol solution is added to the reaction mixture to terminate
the reaction. Then, the reaction product is filtered to obtain some
precipitate. The precipitate is washed with ethanol and dried at
50.degree. C. in a vacuum oven overnight to obtain the final
product, styrene polymer. The results of polymerizations conducted
in the presence of the metallocene catalysts according to the
examples 1 to 9, and natures of the produced polymers are shown in
Table 2 for each catalyst. The produced polymers are extracted
under reflux of methylethylketone for 12 hours, thereby obtaining
polymers which remain without dissolving. These polymers are
analyzed by a carbon NMR spectroscopic investigation method, and it
is found that the polymers have the syndiotatic structure.
Comparative Example 4
[0102] In this example, all the process steps and most of the
materials are the same as used in the example 11 except the
catalyst used. According to this example, a conventional catalyst
Cp*Ti(OMe).sub.3 is used. Polymerization results obtained using the
conventional catalyst Cp*Ti(OMe).sub.3 and the nature of the
resultant polymer are shown in Table 2.
Comparative Example 5
[0103] In this example, all the process steps and most of the
materials are the same as used in the example 11 except the
catalyst used. According to this example, a conventional catalyst
Cp*Ti(OCH.sub.2CH.sub.2)N is used. Polymerization results obtained
using the conventional catalyst Cp*Ti(OCH.sub.2CH.sub.2)N and the
nature of the resultant polymer are shown in Table 2.
TABLE-US-00002 TABLE 2 Results of polymerization of styrene in bulk
phase Distri- bution Activity Molec- Of Molec- (kg PS/ ular ular
Melting Yield molTi Weight Weight Temp. Catalyst (g) hr) (Mw)
(Mw/Mn) (.degree. C.) 2 69.2 1384 623,000 2.1 269 4 68.8 1376
674,000 1.9 270 6 67.4 1380 594,000 2.1 269 Comparative Example 4
64.0 1280 567,000 2.3 269 Cp*Ti(OMe).sub.3 Comparative Example 5
47.9 958 581,000 2.0 270 Cp*Ti--(OCH.sub.2CH.sub.2).sub.3N
[0104] Referring to tables 1 and 2, it is found that the styrene
polymers produced using the half metallocene catalysts according to
the present invention have excellent syndiotacticity, high melting
point and broad molecular weight distribution.
[0105] The metallocene catalyst according to the present invention
provides at least the following advantages.
[0106] First, the metallocene catalyst composed of i) a transition
metal center selected from Groups 3 to 10 in the periodic table,
ii) a cycloalkanedienyl group, and iii) either a triethanolamine
compound or an N-alkyldiethanolamine compound, both of which have a
plurality of binding sites and high steric hinderance, constitutes
a high activity catalyst system together with a cocatalyst such as
alkyl aluminum oxane, thereby rendering syndiotatic styrene
polymers and/or styrene-olefin copolymers capable of being
produced.
[0107] Second, the metallocene catalyst according to the present
invention is capable of producing polymer having high heat
resistance, high chemical resistance, and high processibility, so
that the polymer produced using the metallocene catalyst according
to the present invention can be diversely applied to engineering
plastics.
[0108] In concluding the detailed description, those skilled in the
art will appreciate that many variations and modifications can be
made to the preferred embodiments without substantially departing
from the principles of the present invention. Therefore, the
disclosed preferred embodiments of the invention are used in a
generic and descriptive sense only and not for purposes of
limitation.
* * * * *